Process of separating emulsions



Patented Jan. 13, 1931 UNITED STATES PATENT OFFICE FRANZ BUIDOLF MOSER, OF BUSB'UM, NETHERLANDS, ABSIGNOB TO N. V. DE BATE-AF- SOHE PETROLEUM MAA'ISGHAIPIJ, OF THE HAGUE, NETHERLANDS QBOOESS OF SEPABATING EMULSIONS No Drawing. Application filed September 8, 1924, Serial No. 785,721, and in the Netherlands July 19, 1924.

My invention relates to a material for the separation of petroleum oil emulsions and the liieilas well as to a process for the separation 0' t materials have been proposed with which more or less favorable results were obtained. But a wholly satisfactory solution of this diificult and important problem has nothitherto been found, since the results were ofteii not satisfactory and the materials enipkged were in some cases too expensive.

ccording to my invention a material is prepared for the separation of petroleum oil emulsionsand the like by exposmg high boiling fractions of petroleum, after removal of the substances which easily resinify, to the action of sulphuric acid or oleum (i. e. a concentrated sulfonating reagent), preferably with stirring, and by separating the formed products from the unaltered constituents.

A ve favorably acting reagent is obtained i the products produced according to my invention are separated from adhering oil by dissolving the reagent in water and (if desired) purifying by precipitation of the colloids or by dialysis.

I have further found that the roducts accordin to my invention could e dried by steam eating and also could be pulverized which is especially of advantage for the transportation of my new material.

The active constituent of the new material ap ears to be that part of the non-resinous acid tar which has the property of forming colloidal solutions in water. The ordinary acid tar which is obtained in the refining of lubricating oils by treating same with sulphuric acid contains only traces of these materials. If thesulphuric acid, during refining, is used in installments then the acid tar which is formed and separated from the oil by the addition of the first portions is almost entirely free from products soluble in water, so long as resinous materials are bein produced. These colloidally watersolu le materials are only formed in large quantities after the removal of the easily resinifying constituents of the oil. By applying oleum instead of sulphuric acid the ese emulsions. For this-purpose various yield is considerably increased, perhaps because oleum is a more powerful sulfonatin rea nt. Thus products can be prepared wit out difiiculty which consist for the greaterfiart of hydrophile colloids.

' y the action of sulphuric acid on low boiling petroleum fractions such as the gasoline and kerosene fractions obtained which are also soluble in water but these are not colloidal, or only a small proportion thereof is colloidal and their influence on crude oil emulsions is of no importance. When treating the higher fractlons of petroleum with sulphuric acid, products are.obtained of which the constituent which is soluble in water consists for the greater part of hydrophile colloids which have at products I are the same time the ability to exert a strong surface action.

It has already been fproposed to make use of alkali-metal salts o sulphonated mineral oils for the same purpose.

According to my invention the considerable advantage is obtained that the products are easier to manufacture and besides produce a far greater and more perfect separation of the water from the emulsions.

Acid tar formed in refining kerosene has already been applied too, and particularly as a carrier for sulphuric acid which was used because of its coagulating action to break up the emulsion.

According to the present invention the desired result is obtained by the application of the colloids present in the acid sludge. Whether or not free sulphuric acid is present therein is of no im ortance.

My invention is elucldated by the following exam les of the process:

A distil ate consisting of light machine oil is previously treated with 35% H of 66 B. The resin formed is removed, after which the oil preferably while cooling, is treated with oleum of 20% strength, in quantities of 10-20%. This treatment is continued till the specific gravit of the oil only decreases very slightly. is is the case with most lubricatin oil distillates when about fifty per cent 0 the oil has been conv sumed.

The reaction products settled out and col- :ted amount to about double the weight of e oleum employed. These products, while irring and if desired also while heating, e dissolved in about twice their weight of ater. The excess of oil remains floating on ie surface and is removed. Salt (e. g. aCl) is added to the solution in installents and under stirring until all colloids We been precipitated and the solution is :arly decolorized. By repeating this treatent, the purity can be regulated at will. he precipitated colloidal -material forms 1e reagent used for treating emulsions. he unpurified dark solution (i. e. without lding the salt) can also be applied for the :paration of the emulsions. By the prepitation from the solution and subsequent urification of the precipitate, however, a Lore active, more concentrated product is )tained which can be freed from sulphuric aids by dialysis. It is of great importance lat by drying by steam heating an easily 'ansportable product is obtained that has st nothing of its solubility in water and its :tivity.

The sulphonated compounds produced by llS process, in the preferred form, are not aadily soluble in water, to give clear solu- .ons, they do however, readily give colloidal )lutions in water; they are not soluble in etroleum oils, they are soluble in alcohol nd acetone. They do not form phenols by 1e alkali fusion process.

I-claim:-

1. A process which comprises treating peroleum-and-water emulsions with a colloial material obtained by treating mineral abricating oil substantially free from subtances liable to resinify, with strong sul- IhllIlG acid in excess, diluting the sludge vith water, removing unaltered oil thererom, whereby an aqueous liquid containing olloidal matter results.

2. A process for the manufacture of a material suitable for the separation of peroleum oil emulsions which comprises treatng with strong sulphuric acid, a mineral u ricating oil material containing subtances which can resinify when the oil is reated with sulphuric acid, to remove such :onstituents as easily resinify, and there- Lfter exposing the oil to the action of an :xcess of strong sulphuric acid, thereafter :eparating the products formed from the inaltered oily constituents of the sludge, and ecovering a colloidal material in said :ludge.

3. A process for the manufacture of a ma- .erial suitable for the separation of petroleum )il emulsions which comprises treating with itrong sulphuric acid, a mineral lubricating )il material containing substances which can resinify when the oil is so treated with sulphuric acid, to remove such constituents as easily resinify, and thereafter exposing the oil to the action of an excess of oleum, thereafter diluting the sludge and separating colloidal reaction products which form colloidal suspensions in water, from the unaltered oily constituents in the sludge.

4:. A process of treating high boiling mineral oil having a boiling point range and viscosity suitable for use as lubricating oil, containing a substantial amount of substances which arecapable of resinification, upon treatment with sulphuric acid, which comprises treating the oil with strong sulphuric acid until such substances capa le of resinification are removed from the oil, thereafter treating the residual oil with an excess of concentrated sulphuric acid, separating the sulphonated products from the unaltered oil, and purifying the colloidally water-soluble constituents of the sulphonated products.

5. A process of treating high'boiling mineral oil containing a substantial amount of substances which are capable of resinification, upon treatment with sulphuric acid, which comprises treating the oil with strong sulphuric acid until such substances capable of resinification are removed from the oil, thereafter treating the residual oil with several successive batches of concentrated sulphuric acid, the whole of said acid representing an excess, separating the sulphonated products from the unaltered oil, and

purifying the colloidally water-soluble constituents of the sulphonated products.

6. A process of breaking petroleum oil emulsions which comprises adding theretoa treating reagent comprising a colloidal material. such reagent being obtained by first removing from high boiling fractions of petroleum, any constituents thereof which easily resinify, thereafter subjecting the remaining oil while substantially free from' easily resinifying constituents to the action of an excess of strong sulphuric acid, and thereafter separating a material containing the colloidal products formed from-the unaltered oily constituents.

7. A process of breaking petroleum oil emulsions which comprises adding thereto a treating reagent comprising a colloidal material, such reagent being obtained by first removing from high boiling fractions of petroleum, any constituents thereof which easily resinify, thereafter subjecting the remaining oil while substantially free from easily resinifying constituents to the action of an excess of oleum, and thereafter separating a material containing the colloidal products formed from the unaltered oily constituents.

8. A process of breaking petroleum oil emulsions which comprises adding thereto a treating reagent formed by resinifying some of the constituents of a high boiling mineral oil, removing the resini ed material and treating the oil with strong sulphuric acid 

